Practical Ligand-Enabled N 2 Adsorption of Rhenium(I) Carbonyl Complexes Based on Meridionally Coordinated Terpyridine

作者：Zhiqiang Wang, Zicheng Zhao, Yiheng Zhang, Min Kou, Xianglei Kong, Jia‐Bi Ma · 发表于：The Journal of Physical Chemistry Letters · 年份：2025 · DOI：10.1021/acs.jpclett.5c03289 · 被引用次数：2 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Environmental remediation with nanomaterials、Nanomaterials for catalytic reactions

The prerequisite for N 2 activation under mild conditions is the efficient adsorption of N 2 onto metal sites. Understanding the selectivity and environmental dependence of N 2 adsorption is essential for elucidating fundamental mechanisms and designing efficient catalysts. In this study, we synthesized the complex mer, cis -Re(tpy-κ 3 N )(CO) 2 Cl (where tpy stands for terpyridine) and investigated its reactivity toward N 2 using electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) calculations. Using ESI, the species [Re(tpy)] +, [Re(tpy)(CO)] + and [Re(tpy)(CO) 2 ] + were generated and subsequently allowed to react with N 2 . The mass spectrometry experiments revealed the reactivity order of N 2 adsorption as: [Re(tpy)] + > [Re(tpy)(CO)] + ≫ [Re(tpy)(CO) 2 ] + (inert). DFT calculations indicate the presence of π back-donation between the Re atom and N 2 . The observed decrease in reactivity can be attributed to two primary factors: (i) electron depletion at the Re center by CO ligands, which diminishes its π back-donation capacity, and (ii) steric hindrance from CO ligands, which hinders N 2 access to the preferred planar coordination site. This work provides key insights into the synergistic effects between organic ligands and transition metals, advancing the rational design of molecular systems for N 2 adsorption and activation.